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@PHDTHESIS{Amrhein:638426,
author = {Amrhein, Tim},
othercontributors = {Weinelt, Martin and Kuch, Wolfgang},
title = {{U}ltrafast 4f multiplet excitation in rare-earth metals
studied with {X}-rays},
school = {FU Berlin},
type = {Dissertation},
reportid = {PUBDB-2025-04055},
pages = {125},
year = {2025},
note = {Dissertation, FU Berlin, 2025},
abstract = {Optically driven fundamental processes initiating ultrafast
magnetization dynamics in 4f rare-earth metals have been
studied for many years. Attempts were made to explain the
various demagnetization timescales observed for different 4f
metals, considering e.g. magnon generation or
electron-phonon driven spin-flip scattering. Excitations
within the 4f electronic system, though, were not involved
in the discussion, since they are not directly accessible by
optical stimuli. This thesis reports on time-resolved
experiments performed at the freeelectron laser facilities
EuXFEL and FLASH which identified an up to now disregarded
mechanism provoking 4f electronic excitations on ultrafast
timescales indirectly via interaction with the laser-excited
5d6s valence electrons in 4f metals. By analyzing ultrafast
spectral changes in X-ray absorption (XAS) and resonant
inelastic X-ray scattering (RIXS) signals from terbium metal
with the help of atomistic simulations, inelastic 5d-4f
electron-electron scattering is found to transfer energy and
angular momentum between the 4f and 5d systems. As a
consequence, 4f electrons are excited from the ground state
7F6 into energetically higher 7FJ multiplets. Based on these
findings, a three-temperature model has been developed,
separating temperatures for the 4f electrons, the 5d valence
electrons and the lattice. By fitting the simulation based
on the three-temperature model to the experimental data, the
coupling between 4f and 5d electrons is found to increase
with the amount of valence electrons, able to distribute
enough energy to lift the 4f electronic system to the
energetically lowest excited 4f multiplet 7F5. According to
the 3rd rule of Thole and van der Laan, the absorption
branching ratio of M5 to M4 decreases with the reduction of
the total angular momentum J, as expected for transitions
into energetically higher multiplets 7FJ=5,4,..0 of the 4f
electronic system. With time-resolved XAS experiments at the
FemtoSlicing facility BESSY II, it was demonstrated, that
this correlation can be used to probe and evaluate 4f
multiplet excitations, even with sources exhibiting limited
energy resolution. The reported 5d-4f scattering mechanism
transiently alters the magnetocrystalline anisotropy and
hence the coupling of the 4f system to the lattice. With up
to $22\%$ of all probed atoms being excited to energetically
higher multiplets, inelastic 5d-4f scattering is deemed to
have a significant impact on the ultrafast demagnetization
in terbium metal and must be taken into account for a full
description of the magnetization dynamics in rare-earth
metals.},
cin = {DOOR ; HAS-User},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G2 - FLASH (DESY) (POF4-6G2)},
pid = {G:(DE-HGF)POF4-6G2},
experiment = {EXP:(DE-H253)F-PG1-20150101},
typ = {PUB:(DE-HGF)11},
urn = {urn:nbn:de:kobv:188-refubium-48744-7},
doi = {10.3204/PUBDB-2025-04055},
url = {https://bib-pubdb1.desy.de/record/638426},
}